The 2007 National League Division Series (NLDS), the opening round of the 2007 National League playoffs, began on Wednesday, October 3 and ended on Saturday, October 6, with the champions of the three NL divisions and one wild card team participating in two best-of-five series. They were:

Colorado earned the wild card after winning a one-game playoff with San Diego. Although the division winner with the best record normally plays the wild card team, the Diamondbacks played the Cubs, rather than the wild card Rockies, because the league does not pair teams from the same division against each other in the division series.

Both series represented the first time the opponents had met in the postseason, and the Rockies' victory was their first in any postseason series. The Diamondbacks and the Rockies met in the NL Championship Series, with the Rockies becoming the National League champion and going on to face the American League champion in the 2007 World Series. This was the first time under the expanded playoffs format first used in 1995 that two teams from the National League's Western Division had played against one another in the NLCS.

Eighteen-game winners Carlos Zambrano and Brandon Webb matched each other pitch for pitch in the opening game of the series. Stephen Drew's fourth-inning home run stood as the game's only run until Ryan Theriot's run-scoring single in the sixth tied the game. Unfortunately for Chicago, that would be all their offense as Carlos Mármol would take the loss, allowing a home run to Mark Reynolds and a sacrifice fly to Conor Jackson in relief of Zambrano. José Valverde threw a hitless ninth inning to save the game for Arizona.

Three solo home runs from Chris Young, Eric Byrnes, and Stephen Drew behind six innings pitched (one run on five hits) from Liván Hernández, and four double plays turned on defense put Game 3 out of reach for the Chicago Cubs who were swept out of the post-season by the Arizona Diamondbacks.

Seventeen and fifteen-game winners Jeff Francis and Cole Hamels began the 2007 postseason by retiring the side in order. The face of the game quickly changed in the second frame when Todd Helton tripled to center field in his first career postseason plate appearance. RBI hits by Garrett Atkins and Yorvit Torrealba and a bases-loaded walk by rookie Troy Tulowitzki earned the Rockies a three-run lead that was never relinquished. Matt Holliday homered in the eighth inning to provide insurance after consecutive home runs by Aaron Rowand and Pat Burrell to lead off the Phillies' half of the fifth. The Phillies wasted an ultimately solid effort from Hamels, who walked four in 62⁄3 frames but did not allow a hit after the decisive second inning. Manny Corpas picked up the save for Colorado.

Troy Tulowitzki and Matt Holliday hit consecutive one-out home runs in the first inning off Phillies rookie starter Kyle Kendrick to set the tone for Game 2. The Rockies' runs were quickly answered by virtue of Jimmy Rollins' lead-off home run; Rockies starter Franklin Morales, coming off his own rookie season, would then surrender the lead in the second inning to run-scoring hits from Rollins and catcher Carlos Ruiz. That lead then vanished two innings later when Kaz Matsui hit a two-out grand slam off Phillies reliever Kyle Lohse. Philadelphia loaded the bases in the eighth inning, but Manny Corpas earned a four-out save in stranding all three runners, sealing the Rockies' 10–5 victory. Matsui was a single short of hitting for the cycle.

Not even a computer malfunction plunging Coors Field into darkness for fourteen minutes could stop the roll the Rockies had been on since the middle of September. Kazuo Matsui got the Rockies on the board in the bottom of the fifth with an RBI triple, scoring Yorvit Torrealba from first with the game's first run. Shane Victorino broke the Phillies scoring drought with a solo home run to right in the top of the seventh. After being released mid-season by the Red Sox, J. C. Romero became one of the most reliable bullpen arms for the Phillies down the stretch by not giving up a single run in 152⁄3 innings pitched in September. Unfortunately for Philadelphia in Game 3, Romero faltered and surrendered the go-ahead run by Jeff Baker in the bottom of the eighth. Manny Corpas came on to nail down his third consecutive save in the ninth, sealing the series sweep. The last time Philadelphia was swept in a postseason series is 1976 NLCS, in which Cincinnati beat them, 3–0.